|Número de publicación||US4128526 A|
|Tipo de publicación||Concesión|
|Número de solicitud||US 05/753,862|
|Fecha de publicación||5 Dic 1978|
|Fecha de presentación||23 Dic 1976|
|Fecha de prioridad||23 Dic 1976|
|También publicado como||DE2757323A1|
|Número de publicación||05753862, 753862, US 4128526 A, US 4128526A, US-A-4128526, US4128526 A, US4128526A|
|Inventores||Willem F. H. Borman|
|Cesionario original||General Electric Company|
|Exportar cita||BiBTeX, EndNote, RefMan|
|Citas de patentes (11), Citada por (113), Clasificaciones (18)|
|Enlaces externos: USPTO, Cesión de USPTO, Espacenet|
This invention relates to novel thermoplastic copolyesters prepared by the interesterification of (a) diaromatic acids and diols and/or reactive derivatives thereof or terminally-reactive straight, branched or dicyclic poly(alkylene glycol aromatic acid esters) and (b) a di-ester comprising an aromatic diol.
Poly(alkylene glycol aromatic acid esters) have found use in molding resins because of their rigidity, good dimensional stability, low water absorption and good electrical properties. These resins also produce molded articles having high heat resistance, inherent lubricity and excellent chemical resistance. One restriction on the use of these valuable resins, however, is the fact that the impact strengths of moldings tend to be somewhat inadequate for applications where the molded part is likely to be subjected to severe service conditions. This has led to work to upgrade these properties of poly(alkylene glycol aromatic acid esters) because, both in straight, branched and cyclic alkylene chain modifications, they are so superior to many other molding materials, especially with respect to surface gloss when molded.
It has now been discovered that if poly(alkylene glycol aromatic acid ester) resins are chemically modified by being segmented in a copolyester in which the major portion of the repeating units are (a) poly(alkylene glycol aromatic acid ester) units and the minor portion of the repeating units are units of (b) a di-ester comprising an aromatic diol, then the resulting copolyesters will have enhanced impact resistance, compared to the resin (a) itself. The improvement in impact resistance is achieved with minimal loss of other physical properties and is accompanied with a measurable increase in toughness. It is believed that the presence of the internal units of other aromatic di-esters modifies the rate at which such poly(alkylene glycol aromatic ester) resins crystallize from the melt in a very desirable manner.
Illustratively, if certain aromatic diol-containing di-esters are added to the reactor during the preparation of poly(1,4-butylene terephthalate) by ester interchange between dimethyl terephthalate and 1,4-butanediol, either as part of the initial charge, or after the prepolymerization stage is complete, or if they are reacted with a terminally-reactive poly(1,4-butylene terephthalate) resin, there is caused a most desirable modification in the properties of the resulting, modified polyester molding resins.
By way of illustration, succinic anhydride and maleic anhydride are each reacted, respectively, with bisphenol-A to produce carboxyl-terminated di-esters, and these are used as the source of units. These carboxyl-terminated di-esters are added, respectively, to a reactor with 1,4-butanediol and dimethyl terephthalate and dibutyl tin dilaurate and heated under moderate, then high vacuum until the formation of copolyester is substantially complete. Alternatively, 1,4-butanediol and dimethyl terephthalate can be heated to form β-hydroxyethyl terephthalate, the di-ester added, and the copolyester is formed on further heating. In still another procedure, the di-ester derived from the aromatic diol is reacted with high molecular weight poly(1,4-butylene terephthalate) having functionally reactive end groups, and a small amount of 1,4-butanediol and copolymerization occurs.
No matter how they are made, however, after completion of the reaction and molding the copolyesters, the articles obtained are improved in toughness and reduced in notch sensitivity as compared to bars molded from the corresponding unmodified poly(alkylene aromatic acid esters). There is insubstantial loss in flex modulus and strength.
The effect on crystallization behavior is also noteworthy. The aromatic diol-derived di-ester components significantly reduce the crystallization rate of the molding resin. This is desirable, since it allows longer time for the polymer melt to flow through thin walled sections of a mold before the cooling product solidifies.
In addition to their use in injection molding application, the di-ester coreactants have also been found to be beneficial in improving the properties of poly(alkylene glycol aromatic acid ester) resins used in other applications, such as profile extrusion, extrusion-and injection blow molding, thermoforming, foam molding; in these cases small amounts of ester-forming branching agents may be added to enhance the melt elasticity properties of the products for easier processing.
The copolyester products can also be converted to valuable modifications by adding reinforcing fillers, such as glass fibers, talc, and the like, and/or flame retardant agents such as monomolecular or polymeric halogenated aromatic compounds, with and without flame retardant synergists, such as antimony compounds, or phosphorus compounds, and the like. Surprisingly, the increased toughness of the new copolyesters compensates for the greater brittleness usually induced by the incorporation of such non-soluble additives and fillers.
According to this invention, there are provided novel thermoplastic copolyesters which comprise units derived from:
(a) (i) a dicarboxylic acid selected from one or more of the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, phenyl indane dicarboxylic acid and compounds of the formula: ##STR1## in which X is alkylene of from 1 to 4 carbon atoms, carbonyl, sulfonyl, oxygen or a bond between the benzene rings, or a reactive-derivative thereof, and
(ii) one or more straight chain, branched chain or cyclic aliphatic diols of from 2 to 10 carbon atoms or a reactive-derivative thereof, or
(iii) a terminally-reactive polyester derived from (i) and (ii); and
(b) a terminally-reactive di-ester of an aromatic diol of from 6 to 30 carbon atoms, said units being connected by interterminal linkages consisting essentially of ester linkages.
It is essential that the modified polyester products be prepared in such a way that there is a reaction of terminally-reactive groups as between components (a) and (b). The terminal groups can be in the glycol or aromatic diacid monomer of component (a), in prepolymer thereof, or in resinous higher condensation products comprising component (a). The terminal groups can comprise hydroxyl, carboxyl, carboalkoxy, and the like, including reactive derivatives thereof. The result of reaction between two terminally-reactive groups, of course, must be an ester linkage. After initial mixing, polymerization is carried out under standard conditions, e.g., a first stage, if monomers comprise component (a) at from 150° to 210° C. and a mild vacuum, e.g., 1 to 20 mm. of Hg, and a second stage (first, if a prepolymer or resinous poly(alkylene glycol aromatic diester) is used as component (a), at a higher temperature, e.g., 220° to 280° C., in a high vacuum, e.g., 0.1 to 2 mm. Hg, to form the copolymerizate of this invention.
Component (a) is preferably a mixture or an esterification product of terephthalic acid or isophthalic acid or a reactive derivative thereof or a mixture thereof, and one or more alkylene glycols. The alkylene glycols can be straight chain, branched chain, or alicyclic in nature. Illustratively, the glycol can be ethylene glycol, 1,3-propanediol, 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 1,9-nonanediol; 1,10-decanediol; neopentyl glycol; 1,4-cyclohexanediol; 1,4-cyclohexane dimethanol, a mixture of any of the foregoing, or the like.
The di-esters designated (b) are most preferably derived from an aromatic diol or a reactive derivative thereof and a dibasic acid or reactive derivative thereof, such as an anhydride. Also useful would be the reaction product of an aromatic alcohol of mixed ester forming functionality such as p-hydroxybenzoic acid, or a reactive derivative thereof, and a dibasic acid or reactive derivative thereof, such as an anhydride, although this is not, in a strict sense, a di-ester, per se.
The di-esters designated component (b) preferably will contain at least one carboxy or carboalkoxy terminal group.
In a preferred family of di-ester component (b), the aromatic diol is represented by the formulas: ##STR2## wherein X is alkylene or alkylidene of from 1 to 4 carbon atoms, carbonyl, sulfonyl, oxygen or a bond between the benzene rings, X1, X2 and X3 are selected from hydrogen, C1 -C6 alkyl, chlorine or bromine, and p, q and r are from 1 to 4.
Illustrative of the aromatic diols useful in component (b) are: bisphenol-A, hydroquinone, resorcinol, 3,3',5,5'-tetramethyl-4,4'-bisphenol, tetrabromobisphenol-A, tetrachlorobisphenol-A, and the like. Illustrative of the acids used to form the ester forming adducts in component (b) are phthalic acid or anhydride, tetrabromophthalic acid or anhydride, succinic acid or anhydride, maleic acid or anhydride, and the like. Preferred components (b) are derived from bisphenol-A and succinic anhydride and from bisphenol-A and maleic anhydride, by means to be exemplified hereinafter.
The copolyesters of this invention preferably comprise from 95 to 50 parts by weight of the units of poly(alkylene glycol aromatic diacid esters), preferably poly(1,4-butylene terephthalate). The polyester component will preferably have an intrinsic viscosity of above 0.1 dl./g. and preferably, between 0.1 and 0.5 dl./g. as measured in a 60:40 mixture of phenol/tetrachloroethane at 30° C. The balance, 5 to 50 parts by weight of the copolyester will comprise units of component (b).
As will be understood by those skilled in this art, the poly(alkylene glycol aromatic acid ester) units (a) can be straight chain or branched, e.g., by use of a branching component, e.g., 0.05 to 3 mole %, based on aromatic ester units, of a branching component which contains at least three ester-forming groups. This can be a polyol, e.g., pentaerythritol, trimethylolpropane, and the like, or a polybasic acid compound, e.g., trimethyl trimesate, and the like.
The copolyesters may be employed as such in the fabrication of molded articles or they may be blended with other polymers, especially preferably poly(1,4-butylene terephthalate) straight chain or branched (as described), and with stabilizers, reinforcing agents and/or flame retardant additives.
Suitable reinforcing agents are well known but, illustratively, they may be selected from the group consisting of metals, such as aluminum, iron or nickel particles and the like, and non-metals, such as carbon filaments, silicates, such as acicular calcium silicate, asbestos, titanium dioxide, potassium titanate and titanate whiskers, wollastonite, glass flakes and fibers. It is also to be understood that unless the filler adds to the strength and stiffness of the composition, it is only a filler and not a reinforcing filler as contemplated herein.
Although it is only necessary to have at least a reinforcing amount of the reinforcement present, in general the reinforced compositions will comprise from 10 to 80% by weight of the total composition of the reinforcing agent.
In particular, the preferred reinforcing fillers are of glass, and it is usually preferred to employ fibrous glass filaments comprised of lime-aluminum borosilicate glass that is relatively soda free. This is known as "E" glass. However, other glasses are useful where electrical properties are not important, e.g., the low soda glass known as "C" glass. The filaments are made by standard processes, e.g., by steam or air blowing, flame blowing and mechanical pulling. The filament diameters range from about 0.00012 to 0.00075 inch, but this is not critical to the present invention. Glass fibers may be surface coated in accordance with standard procedures to improve their reinforcing performances. In general, best properties will be obtained from reinforced compositions that contain from 20 to 30 percent by weight of the glass reinforced composition.
The length of glass filaments and whether or not they are bundled into fibers and the fibers bundled in turn to yarns, ropes or rovings, or woven into mats, and the like, are also not critical to the practice of the invention. In preparing the present compositions, it is convenient to use the filamentous glass in the form of chopped strands of from about 1/8 inch to about 1 inch long, preferably less than 1/4 inch long. In articles that are molded from the compositions of the invention, even shorter lengths will be encountered because, during compounding, considerable fragmentation will occur. This is desirable, however, because the best properties are exhibited by thermoplastic injection molded articles in which the filament lengths lie between about 0.000005 inch and 0.12 (1/8 inch).
The present invention also contemplates flame retardant compositions comprising the new copolyesters with or without reinforcing agent. Illustrative flame retardants are disclosed in U.S. Pat. Nos. 3,833,685, 3,341,154, 3,915,926 and 3,671,487 which are hereby incorporated by reference. Other flame retardants are disclosed in U.S. Pat. Nos. 3,681,281, and 3,557,053, 3,830,771 and U.K. Pat. No. 1,358,080, all of which are incorporated by reference.
In general, the flame retardant additives useful in this invention comprise a family of chemical compounds well known to those skilled in the art. Generally speaking, the more important of these compounds contain chemical elements employed for their ability to impart flame resistance, e.g., bromine, chlorine, antimony, phosphorus and nitrogen. It is preferred that the flame retardant additive comprises a halogenated organic compound (brominated or chlorinated); a halogen-containing organic compound in admixture with antimony oxide; elemental phosphorus or a phosphorus compound; a halogen-containing compound in admixture with a phosphorus compound or compounds containing phosphorus-nitrogen bonds or a mixture of two or more of the foregoing.
The amount of flame retardant additive used is not critical to the invention, so long as it is present in a minor proportion based on said composition -- major proportions will detract from physical properties -- but at least sufficient to render the block polyester resin non-burning or self-extinguishing. Those skilled in the art are well aware that the amount will vary with the nature of the resin and with the efficiency of the additive. In general, however, the amount of additive will be from 0.5 to 50 parts by weight per 100 parts of resin. A preferred range will be from about 3 to 40 parts and an especially preferred range will be from about 8 to 40 parts of additive per 100 parts of resin. Smaller amounts of compounds highly concentrated in the elements responsible for flame retardance will be sufficient, e.g., elemental red phosphorus will be preferred at 0.5 to 2.0 parts by weight per 100 parts of resin, while phosphorus in the form of triphenyl phosphate will be used at 25 parts of phosphate per 100 parts of resin, and so forth. Halogenated aromatics will be used at 8 to 50 parts and synergists, e.g., antimony oxide will be used at about 2 to 5 parts by weight per 100 parts of resin.
Among the useful halogen-containing compounds are those of the formula: ##STR3## wherein R is an alkylene, alkylidene or cycloaliphatic linkage, e.g., methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene, and the like; a linkage selected from the group consisting of ether; carbonyl; amine; a sulfur-containing linkage, e.g., sulfide, sulfoxide, sulfone; a phosphorus-containing linkage; and the like. R can also consist of two or more alkylene or alkylidene linkages connected by such groups as aromatic, amino, ether, carbonyl, sulfide, sulfoxide, sulfone, a phosphorus-containing linkage, and the like. Other groups which are represented by R will occur to those skilled in the art.
Ar and Ar' are mono- or polycarbocyclic aromatic groups such as phenylene, biphenylene, terphenylene, naphthylene, and the like. Ar and Ar' may be the same or different.
Y is a substituent selected from the group consisting of organic, inorganic, or organometallic radicals. The substituents represented by Y include (1) halogen, e.g., chlorine, bromine, iodine, or fluorine or (2) ether groups of the general formula OE, wherein E is a monovalent hydrocarbon radical similar to Z or (3) monovalent hydrocarbon groups of the type represented by R or (4) other substituents, e.g., nitro, cyano, etc., said substituents being essentially inert provided there be at least one and preferably two halogen atoms per aryl, e.g., phenyl nucleus.
Z is a monovalent hydrocarbon group exemplified by the following: alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, decyl, and the like; aryl groups, such as phenyl, naphthyl, biphenyl, xylyl, tolyl, and the like; aralkyl groups, such as benzyl, ethylphenyl, and the like; cycloaliphatic groups such as cyclopentyl, cyclohexyl, and the like; as well a monovalent hydrocarbon groups containing inert substituents therein. It will be understood that where more than one Z is used, they may be alike or different.
The letter d represents a whole number ranging from 1 to a maximum equivalent to the number of replaceable hydrogens substituted on the aromatic rings comprising Ar or Ar'. The letter e represents a whole number ranging from 0 to a maximum controlled by the number of replaceable hydrogens on R. The letters a, b and c represent whole numbers including 0. When b is not 0, neither a nor c may be 0. Otherwise either a or c, but not both, may be 0. Where b is 0, the aromatic groups are joined by a different carbon-carbon bond.
The hydroxyl and Y substituents on the aromatic groups, Ar and Ar' can be varied in the ortho, meta or para positions on the aromatic rings and the groups can be in any possible geometric relationship with respect to one another.
Included within the scope of the above formula are biphenyls of which the following are representative:
The preparation of these and other applicable biphenyls are known in the art. In place of the divalent aliphatic group in the above examples may be substituted sulfide, sulfoxy, and the like.
Included within the above structural formula are substituted benzenes exemplified by 1,3-dichlorobenzene, 1,4-dibromobenzene, 1,3-dichloro-4-hydroxybenzene, hexachlorobenzene, hexabromobenzene, and biphenyls such as 2,2'-dichlorobiphenyl, 2,4'-dibromobiphenyl, and 2,4'-dichlorobiphenyl.
Preferred flame retardant additives consist of aromatic carbonate homopolymers having repeating units of the formula: ##STR4## wherein R1 and R2 are hydrogen, (lower)alkyl or phenyl, X1 and X2 are bromo or chloro and m and r are from 1 to 4. These materials may be prepared by techniques well known to those skilled in the art. Also preferred are aromatic carbonate copolymers in which from 25 to 75 weight percent of the repeating units comprise chloro- or bromo-substituted dihydric phenol, glycol or dicarboxylic acid units. See, e.g., A. D. Wambach, U.S. Pat. No. 3,915,926, above-mentioned.
In addition, preferred are aromatic halogen compounds such as chlorinated benzene, brominated benzene, chlorinated biphenyl, chlorinated terphenyl, brominated biphenyl, brominated terphenyl, or a compound comprising two phenyl radicals separated by a divalent alkylene or oxygen group and having at least two chlorine or bromine atoms per phenyl nucleus, and mixtures of at least two of the foregoing.
In general, the preferred phosphorus compounds are selected from elemental phosphorus or organic phosphonic acids, phosphonates, phosphinates, phosphonites, phosphinites, phosphene oxides, phosphenes, phosphites or phosphates. Illustrative are triphenyl phosphine oxide. This can be used alone or mixed with hexabromobenzene or a chlorinated biphenyl and, optionally, antimony oxide.
Typical of the preferred phosphorus compounds to be employed in this invention would be those having the general formula: ##STR5## in which X = S or 0, and n = 0 or 1, Y', Y" and Y'" are the same or different and represent alkyl, cycloalkyl, aryl, alkyl substituted aryl, halogen substituted aryl, aryl substituted alkyl, alkyloxy, cycloalkyloxy, halogen substituted alkyloxy, aryloxy, halogen substituted aryloxy, or halogen. Two of the Y's may be combined into a cyclic structure, or one or two of the Y's may be difunctional in which case the compounds consists of short or long chain compounds containing a plurality of P atoms per molecule. Typical examples of suitable phosphorous compounds include: triphenyl phosphate, diphenyl phenyl phosphonate, phenyl diphenyl phosphinate, triphenyl phosphine, triphenyl phosphine oxide, tris(p-bromophenyl) phosphate, neopentyl phenyl phosphonate, tris(dibromopropyl) phosphate, dibenzyl phenyl phosphonate, poly(1,4 cyclo hexylene dimethylene) phenyl phosphonate, pentaerythritol bis(p bromophenyl) phosphonate, and the like. A preferred flame retardant is tris(tribromophenyl) phosphate.
Also suitable as flame retardant additives for this invention are compounds containing phosphorus-nitrogen bonds, such as phosphonitrilic chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, tris(aziridinyl) phosphine oxide or tetrakis(hydroxymethyl) phosphonium chloride. These flame retardant additives are commercially available.
The following examples illustrate the present invention, but they are not to be construed to limit it in any manner whatsoever. All parts are by weight, unless otherwise indicated.
(a) An adduct of succinic anhydride and 2,2-bis-(4-hydroxy phenyl) propane (BPA) is prepared by reacting 2.5 g. of BPA, 2.4 g. of succinic anhydride and 0.5 ml of triethylamine in 10 ml. of refluxing methylene chloride until all is dissolved. MeCl2 is distilled off and the residue left to solidify. The product is recrystallized from acetone. The reaction product is homogeneous by thin layer chromatography, shows a sharp melting peak at 137° C. by differential scanning calorimetry, and has an infrared spectrum consistent with the assumed structure of BPA disuccinate.
(b) 1.15 g. of 2,2-bis(4-hydroxyphenyl)propane (BPA) and 1.05 g. of succinic anhydride are placed in a 250 × 20 mm cylindrical glass reactor provided with a mechanically driven, hermetically sealed spiral glass stirring rod and distillation attachment for removal of volatile reaction by-products. The reactor is immersed in a silicone oil bath heated to 150° C. for a period of 20 minutes, causing the reactants to melt and coreact. After removing the reactor from the oil bath and cooling its contents, 20 g. of poly(1,4-butylene terephthalate) (PBT) is added. The PBT has an intrinsic viscosity of 0.41 dl./g. as determined in a 60:40 by weight solvent mixture of phenol and sym.-tetrachloroethane at 30° C., and contains a catalyst residue remaining from 0.1 mole % tetra(2-ethylhexyl)titanate added during the preparation of the PBT.
The reactor is again immersed in the oil bath and heated for 35 minutes at a gradually increasing temperature from 200°-233° C. At that time, an increasing vacuum is gradually applied to the reactor contents, while the temperature is raised further, until after 20 minutes the temperature is 252° C. and the vacuum 0.1 mm of mercury.
After addition of 0.1 ml. of 1,4-butanediol to the reaction mixture, the polymerization is continued for 90 minutes at 252° C. and 0.1-0.3 mm Hg. The product, after removal from the reactor, is tough and ductile and has an I.V. of 0.84 dl./g.
The crystallization rate of the material at 200° F. is determined by melting a small particle between microscope coverslips on a hot plate at 450° F. and rapidly transferring it to a microscope hot stage kept at 200° F. between crossed polarizers. The increase in light transmission as the sample crystallizes is measured and recorded. The time to initial crystallization (ti) is 2.1 seconds, and the additional time required to achieve 50% of the final crystallinity (t1/2) is 0.3 seconds. In comparison, a sample of PBT homopolymer has a ti = 1.5 secs. and a t1/2 = 0.2 secs.
Bisphenol-A, 1.15 g. and 1.05 g. succinic anhydride are pre-reacted as in Example 1 and cooled. 18.4 g. of dimethyl terephthalate, 13 g. of 1,4-butanediol, and 0.05 ml. of dibutyl tin dilaurate are added, and the mixture heated 20 minutes at 180° C., 65 minutes at 200° C., and 35 minutes at 220° C. At this time, distillation of methanol has stopped. A vacuum is now applied gradually to the reaction and heating continued for an additional 2 hours, final reaction conditions are 252° C. at 0.05 mm Hg.
The reaction product is removed from the reactor. It has an I.V. of 0.71 dl./g.
The sample has a ti = 9 sec. and t1/2 = 0.3 secs. at 200° F. Differential scanning calorimetry gives a melting peak starting at 187° C. with a maximum of 212° C. and a crystallization peak starting at 186° C. with a maximum at 164° C.
Maleic anhydride, 1.03 g., and 1.15 of BPA are reacted with 20 g. of PBT (I.V. = 0.41 dl./g.) as described in Example 2. The reaction product is quite tough and has an I.V. of 0.865 dl./g.
Among the variations possible in the invention in light of the detailed examples, there can be substituted for 1,4-butanediol, other glycols such as ethylene glycol, 1,4-cyclohexane dimethanol, and the like, and for dimethyl terephthalate, dimethyl isophthalate, dimethyl naphthalene dicarboxylate, and the like, as well as the corresponding prepolymers and terminally-reactive high polymers. For the dibutyl tin dilaurate, there can be substituted other transesterification catalysts, such as zinc salts, antimony oxide or esters, and the like. For the bisphenol-A, there can be substituted other aromatic diols, such as hydroquinone, resorcinol, tetrabromobisphenol-A, and the like. For the succinic anhydride or the maleic anhydride, there can be substituted phthalic anhydride, tetrabromophthalic anhydride, and the like. Reinforced compositions can be obtained by intimately blending, e.g. 30 parts by weight of glass fiber reinforcement with 70 parts by weight of the copolyesters of Examples 1-3. Reinforced, flame retardant compositions can be provided by making an intimate blend comprising 52 parts by weight of the copolyester of Examples 1-3, 30 parts of 1/8 inch long chopped filamentous glass reinforcement, 13 parts by weight of a 1:1 copolycarbonate of bisphenol-A and tetrabromobisphenol-A (27% bromine-modified Procedure A-U.S. Pat. No. 3,936,400) and 5 parts by weight of antimony oxide.
Obviously, other modifications and variations of the present invention are possible in the light of the above teachings. It is, therefore, to be understood that changes may be made in the particular embodiments of the invention described which are within the full intended scope of the invention as defined by the appended claims.
|Patente citada||Fecha de presentación||Fecha de publicación||Solicitante||Título|
|US3047536 *||5 Feb 1957||31 Jul 1962||Dow Chemical Co||Polyesters|
|US3278640 *||11 Mar 1963||11 Oct 1966||Borg Warner||Segmented copolyester comprising aromatic and aliphatic polyester segments|
|US3341154 *||30 Jul 1964||12 Sep 1967||Smith & Sons Ltd S||Control systems for aircraft engine installations|
|US3557053 *||18 Mar 1968||19 Ene 1971||Mobay Chemical Corp||High temperature thermoplastics stabilized with a tris(halophenyl)phosphate,a tris(halonaphthyl) phosphate,a tris(halophenyl)phosphine oxide,a tris(halonaphthyl)phosphine oxide,a polyhalophosphate,a polyhalophenylphosphate,a polyhalonaphthylphosphate,a polyhalophosphate and mixtures thereof|
|US3671487 *||5 May 1971||20 Jun 1972||Gen Electric||Glass reinforced polyester resins containing polytetrafluoroethylene and flame retardant additives|
|US3681281 *||10 Jul 1970||1 Ago 1972||Celanese Corp||Flame-retardant polyesters|
|US3772405 *||2 Feb 1972||13 Nov 1973||Eastman Kodak Co||Process for preparing aromatic diester containing copolyesters and products obtained thereby|
|US3830771 *||25 Jun 1971||20 Ago 1974||Celanese Corp||Phosphorus-containing polyesters|
|US3833685 *||10 Mar 1972||3 Sep 1974||Gen Electric||Flame retardant thermoplastic compositions|
|US3915926 *||23 Jul 1974||28 Oct 1975||Gen Electric||Flame retardant thermoplastic compositions|
|US3936400 *||5 Jul 1974||3 Feb 1976||General Electric Company||Flame retardant foamed polyester compositions|
|Patente citante||Fecha de presentación||Fecha de publicación||Solicitante||Título|
|US5587428 *||7 Jun 1995||24 Dic 1996||Eastern Michigan University||Polymeric vehicle effective for providing solventless coating compositions|
|US5610263 *||7 Jun 1995||11 Mar 1997||Eastern Michigan University||Water thinned polymeric vehicle for coating compositions with low amounts of volatile oragnic compounds|
|US5641854 *||7 Jun 1995||24 Jun 1997||Eastern Michigan University||Polymeric vehicle for high solids coatings|
|US5840798 *||6 Jun 1997||24 Nov 1998||General Electric Company||Glass filled polyester molding composition|
|US5910563 *||10 Nov 1997||8 Jun 1999||Exxon Chemical Patents, Inc.||Water thinned polymeric vehicle for coating compositions with low amounts of volatile organic compounds|
|US5955550 *||10 Nov 1997||21 Sep 1999||Exxon Chemical Patents, Inc.||Polymeric vehicle for providing solventless coating compositions|
|US5969085 *||10 Nov 1997||19 Oct 1999||Exxon Chemical Patents, Inc.||Polymeric vehicle for high solids coatings|
|US5981661 *||29 Ago 1997||9 Nov 1999||General Electric Company||Modified weatherable thermoplastic resin molding compositions and articles molded therefrom|
|US6011125 *||25 Sep 1998||4 Ene 2000||General Electric Company||Amide modified polyesters|
|US6127475 *||25 Sep 1998||3 Oct 2000||General Electric Company||Composition for laser marking|
|US6214916||29 Abr 1998||10 Abr 2001||General Electric Company||Composition for laser marking|
|US6482879||19 Mar 2001||19 Nov 2002||General Electric Company||Composition for laser marking|
|US6486251||29 Feb 2000||26 Nov 2002||General Electric Company||Special visual effect polycarbonate-polyester composition|
|US7435780||29 Nov 2005||14 Oct 2008||Sabic Innovavtive Plastics Ip B.V.||Poly(arylene ether) compositions and methods of making the same|
|US7795320||26 Ene 2007||14 Sep 2010||Sabic Innovative Plastics Ip B.V.||Copolyetheresters derived from polyethylene terephthalate|
|US7799836||21 Sep 2010||Sabic Innovative Plastics Ip B.V.||Process for making polybutylene terephthalate (PBT) from polyethylene terephthalate (PET)|
|US7799838||23 Jul 2007||21 Sep 2010||Sabic Innovative Plastics Ip B.V.||Elastomer blends of polyesters and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom|
|US7799892||2 May 2008||21 Sep 2010||Sabic Innovative Plastics Ip B.V.||Method of making polybutylene terephthalate and compositions and articles comprising the same|
|US7807745||24 Ene 2007||5 Oct 2010||Sabic Innovative Plastics Ip B.V.||Molding compositions containing polycarbonate and modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET)|
|US7829614||9 Nov 2010||Sabic Innovative Plastics Ip B.V.||Reinforced polyester compositions, methods of manufacture, and articles thereof|
|US7847032||10 Dic 2008||7 Dic 2010||Sabic Innovative Plastics Ip B.V.||Poly(arylene ether) composition and extruded articles derived therefrom|
|US7855238||26 Ene 2007||21 Dic 2010||Sabic Innovative Plastics Ip B.V.||Molding compositions containing polyalkylene terephthalates and modified polybutylene terephthalate (PBT) random copolymers derived from PET|
|US7902263||24 Ene 2007||8 Mar 2011||Sabic Innovative Plastics Ip B.V.||Process for making polybutylene terephthalate (PBT) from polyethylene terephthalate (PET)|
|US7902264||8 Mar 2011||Sabic Innovative Plastics Ip B.V.||Polytrimethylene terephthalate (PTT) derived from polyethylene terephthalate (PET) and containing PET residues|
|US7910657||30 Dic 2008||22 Mar 2011||Sabic Innovative Plastics Ip B.V.||Process for the manufacture of polybutylene terephthalate copolymers from polyethylene terephthalate, and compositions and articles thereof|
|US7923506||23 Ene 2007||12 Abr 2011||Sabic Innovative Plastics Ip B.V.||Molding compositions containing modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET)|
|US7928150||19 Abr 2011||Sabic Innovative Plastics Ip B.V.||Process for the manufacture of lonomeric polybutylene terephthalate from polyethylene terephthalate, and compositions and articles thereof|
|US7935737||29 Ene 2007||3 May 2011||Sabic Innovative Plastics Ip B.V.||Articles derived from compositions containing modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET)|
|US8017697||13 Sep 2011||Sabic Innovative Plastics Ip B.V.||Poly(arylene ether)-polysiloxane composition and method|
|US8017716||13 Sep 2011||Sabic Innovative Plastics Ip B.V.||Morpholine-substituted poly(arylene ether) and method for the preparation thereof|
|US8034870||11 Oct 2011||Sabic Innovative Plastics Ip B.V.||Flame-retardant polyester composition|
|US8067493||29 Nov 2011||Sabic Innovative Plastics Ip B.V.||Polymer compositions, method of manufacture, and articles formed therefrom|
|US8084550||27 Dic 2011||Sabic Innovative Plastics Ip B.V.||Low gloss thermoplastic composition|
|US8088834||3 Ene 2012||Sabic Innovative Plastics Ip B.V.||Process for making polybutylene terephthalate (PBT) from polyethylene terephthalate (PET)|
|US8092717||12 Jul 2007||10 Ene 2012||Sabic Innovative Plastics Ip B.V.||Thermoplastic poly(arylene ether) / polyester blends and articles thereof|
|US8110609||7 Feb 2012||Sabic Innovative Plastics Ip B.V.||Copolyetheresters derived from polyethylene terephthalate|
|US8124717||11 Abr 2011||28 Feb 2012||Sabic Innovative Plastics Ip B.V.||Morpholine-substituted poly(arylene ether) and method for the preparation thereof|
|US8129471||30 Dic 2009||6 Mar 2012||Sabic Innovative Plastics Ip B.V.||Polycarbonate-poly(ether-ester) copolymer composition, method of manufacture, and articles therefrom|
|US8138233||4 Feb 2011||20 Mar 2012||Sabic Innovative Plastics Ip B.V.||Process for making polybutylene terephthalate (PBT) from polyethylene terephthalate (PET)|
|US8138244||30 Dic 2008||20 Mar 2012||Sabic Innovative Plastics Ip B.V.||Reinforced polyester compositions, method of manufacture, and articles thereof|
|US8158710||17 Abr 2012||Sabic Innovative Plastics Ip B.V.||Polyester blends, methods of making, and articles formed therefrom|
|US8309655||22 Dic 2009||13 Nov 2012||Sabic Innovative Plastics Ip B.V.||Methods for the preparation of a poly(arylene ether) polysiloxane multiblock copolymer, multiblock copolymers produced thereby, and associated compositions and articles|
|US8309656||23 Jul 2007||13 Nov 2012||Sabic Innovative Plastics Ip B.V.||Elastomer blends containing polycarbonates and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom|
|US8450412||28 May 2013||Sabic Innovative Plastics Ip B.V.||Flame retardant polyamide composition, method, and article|
|US8536272||12 Jul 2007||17 Sep 2013||Sabic Innovative Plastics Ip B.V.||Thermoplastic poly(arylene ether)/polyester blends and method of making|
|US8541505||21 Sep 2009||24 Sep 2013||Sabic Innovative Plastics Ip B.V.||Poly(arylene ether) composition with improved melt flow and method for the preparation thereof|
|US8557158||23 Ago 2011||15 Oct 2013||Sabic Innovative Plastics Ip B.V.||Molded article having enhanced aesthetic effect and method and system for making the molded article|
|US8592523||10 Jul 2008||26 Nov 2013||Sabic Innovative Plastics Ip B.V.||Low gloss thermoplastic articles|
|US8669332||27 Jun 2011||11 Mar 2014||Sabic Innovative Plastics Ip B.V.||Poly(arylene ether)-polysiloxane composition and method|
|US8680167||25 Ene 2007||25 Mar 2014||Sabic Innovative Plastics Ip B.V.||Molding compositions containing fillers and modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET)|
|US8722837||31 Ene 2012||13 May 2014||Sabic Innovative Plastics Ip B.V.||Poly(phenylene ether)-polysiloxane composition and method|
|US8735505||14 Sep 2012||27 May 2014||Sabic Innovative Plastics Ip B.V.||Elastomer blends containing polycarbonates and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom|
|US8877862||15 Jul 2011||4 Nov 2014||Saudi Basic Industries Corporation||Method for color stabilization of poly(butylene-co-adipate terephthalate|
|US8889820||15 Feb 2012||18 Nov 2014||Saudi Basic Industries Corporation||Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof|
|US8895660||1 Mar 2012||25 Nov 2014||Saudi Basic Industries Corporation||Poly(butylene-co-adipate terephthalate), method of manufacture, and uses thereof|
|US8901243||30 Mar 2012||2 Dic 2014||Saudi Basic Industries Corporation||Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof|
|US8901273||15 Feb 2012||2 Dic 2014||Saudi Basic Industries Corporation||Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof|
|US8933162||28 Mar 2012||13 Ene 2015||Saudi Basic Industries Corporation||Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof|
|US8946345||29 Mar 2012||3 Feb 2015||Saudi Basic Industries Corporation||Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst|
|US8969506||15 Feb 2012||3 Mar 2015||Saudi Basic Industries Corporation||Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof|
|US9034983||1 Mar 2012||19 May 2015||Saudi Basic Industries Corporation||Poly(butylene-co-adipate terephthalate), method of manufacture and uses thereof|
|US20030114575 *||10 Dic 2002||19 Jun 2003||General Electric Company||Fiber reinforced thermoplastic composition|
|US20050137297 *||15 Dic 2004||23 Jun 2005||General Electric Company||Flame-retardant polyester composition|
|US20050165207 *||22 Dic 2004||28 Jul 2005||General Electric Company||Polyester molding composition and process for its preparartion|
|US20060264579 *||22 Dic 2005||23 Nov 2006||Ellington Donald H||Low gloss thermoplastic composition|
|US20060270767 *||26 May 2005||30 Nov 2006||Van Gisbergen Josephus Gerardu||Mineral filled polyester polycarbonate composition|
|US20060287429 *||21 Nov 2005||21 Dic 2006||Gaggar Satish K||Glass fiber thermoplastic composite|
|US20070123625 *||29 Nov 2005||31 May 2007||Pravin Dorade||Poly(arylene ether) compositions and methods of making the same|
|US20070173619 *||23 May 2006||26 Jul 2007||Yu Claire Q||Low gloss thermoplastic articles|
|US20070203253 *||24 Ene 2007||30 Ago 2007||Parminder Agarwal||Process for making polybutylene terephthalate (pbt) from polyethylene terephthalate (pet)|
|US20070208160 *||24 Ene 2007||6 Sep 2007||Parminder Agarwal||Process for making polybutylene terephthalate (pbt) from polyethylene terephthalate (pet)|
|US20070213473 *||9 Mar 2006||13 Sep 2007||Yu Claire Q||Composition and method of use|
|US20070225473 *||27 Dic 2006||27 Sep 2007||Michael Determan||Polytrimethylene terephthalate (ptt) derived from polyethylene terephthalate (pet) and containing pet residues|
|US20070225474 *||26 Ene 2007||27 Sep 2007||Michael Determan||Copolyetheresters derived from polyethylene terephthalate|
|US20070244242 *||25 Ene 2007||18 Oct 2007||Parminder Agarwal||Molding compositions containing fillers and modified polybutylene terephthalate (pbt) random copolymers derived from polyethylene terephthalate (pet)|
|US20070275242 *||29 Ene 2007||29 Nov 2007||General Electric Company||Articles derived from compositions containing modified polybutylene terephthalate (pbt) random copolymers derived from polyethylene terephthalate (pet)|
|US20070276069 *||24 Ene 2007||29 Nov 2007||Parminder Agarwal||Molding compositions containing polycarbonate and modified polybutylene terephthalate (pbt) random copolymers derived from polyethylene terephthalate (pet)|
|US20070278462 *||23 Ene 2007||6 Dic 2007||Kristen Cohoon||Molding compositions containing modified polybutylene terephthalate (pbt) random copolymers derived from polyethylene terephthalate (pet)|
|US20080027167 *||23 Jul 2007||31 Ene 2008||General Electric Company||Elastomer blends containing polycarbonates and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom|
|US20080039571 *||26 Ene 2007||14 Feb 2008||Kristen Cohoon||Molding compositions containing polyalkylene terephthalates and modified polybutylene terephthalate (pbt) random copolymers derived from pet|
|US20080125551 *||27 Nov 2006||29 May 2008||General Electric Company||Polyester blends, methods of making, and articles formed therefrom|
|US20080246181 *||7 May 2008||9 Oct 2008||Yantao Zhu||Polymer Compositions, Method of Manufacture, and Articles Formed Therefrom|
|US20080248278 *||2 Abr 2007||9 Oct 2008||General Electric Company||Fiber reinforced thermoplastic sheets with surface coverings and methods of making|
|US20090005477 *||10 Jul 2008||1 Ene 2009||Claire Qing Yu||Low gloss thermoplastic articles|
|US20090014692 *||12 Jul 2007||15 Ene 2009||General Electric Company||Thermoplastic poly(arylene ether) / polyester blends and articles thereof|
|US20090036606 *||12 Jul 2007||5 Feb 2009||General Electric Company||Thermoplastic poly(arylene ether) / polyester blends and method of making|
|US20090069489 *||20 Dic 2007||12 Mar 2009||Peter Vollenberg||Polycarbonate-poly(ester-ether) copolymer composition, method of manufacture, and articles therefrom|
|US20090170985 *||28 Dic 2007||2 Jul 2009||Rina Ai||Polyester-polyamide compositions, articles, and method of manufacture thereof|
|US20090275698 *||2 May 2008||5 Nov 2009||Gomatam Raghavan Ravi||Method of Making Polybutylene Terephthalate and Compositions and Articles Comprising the Same|
|US20090281204 *||12 Nov 2009||Ganesh Kannan||Process for the Manufacture of Ionomeric Polybutylene Terephthalate From Polyethylene Terephthalate, and Compositions and Articles Thereof|
|US20090318635 *||24 Dic 2009||Alvaro Carrillo||Poly(arylene ether)-polysiloxane composition and method|
|US20100139944 *||10 Dic 2008||10 Jun 2010||Hua Guo||Poly(arylene ether) composition and extruded articles derived therefrom|
|US20100168289 *||30 Dic 2008||1 Jul 2010||Ding Tianhua||Reinforced polyester compositions, methods of manufacture, and articles thereof|
|US20100168290 *||30 Dic 2008||1 Jul 2010||Ding Tianhua||Reinforced polyester compositions, method of manufacture, and articles thereof|
|US20100168317 *||30 Dic 2008||1 Jul 2010||Cahoon-Brister Kristen||Poly(butylene terephthalate) compositions, methods of manufacture, and articles thereof|
|US20100168321 *||30 Dic 2008||1 Jul 2010||Cahoon-Brister Kristen||Poly(butylene terephthalate) compositions, methods of manufacture, and articles thereof|
|US20100168328 *||30 Dic 2008||1 Jul 2010||Ganesh Kannan||Process for the manufacture of polycyclohexane dimethylene terephthalate copolymers from polyethylene terephthalate, and compositions and articles thereof|
|US20100168336 *||30 Dic 2008||1 Jul 2010||Kristen Cohoon-Brister||Process for the manufacture of polybutylene terephthalate copolymers from polyethylene terephthalate, and compositions and articles thereof|
|US20110003962 *||6 Ene 2011||Alvaro Carrillo||Morpholine-substituted poly(arylene ether) and method for the preparation thereof|
|US20110003964 *||6 Ene 2011||Parminder Agarwal||Process for making polybutylene terephthalate (pbt) from polyethylene terephthalate (pet)|
|US20110124821 *||26 May 2011||Sabic Innovative Plastics Ip B.F.||Process for making polybutylene terephthalate (pbt) from polyethylene terephthalate (pet)|
|US20110152420 *||22 Dic 2009||23 Jun 2011||Mark Elkovitch||Poly(arylene ether)/polyamide compositions, methods, and articles|
|US20110152431 *||23 Jun 2011||Mark Elkovitch||Flame retardant polyamide composition, method, and article|
|US20110152471 *||23 Jun 2011||Radha Kamalakaran||Methods for the preparation of a poly(arylene ether) polysiloxane multiblock copolymer, multiblock copolymers produced thereby, and associated compositions and articles|
|US20110155975 *||30 Dic 2009||30 Jun 2011||Shreyas Chakravarti||Polycarbonate-poly(ether-ester) copolymer composition, method of manufacture, and articles therefrom|
|US20110184128 *||21 Sep 2009||28 Jul 2011||Hua Guo||Poly(arylene ether) composition with improved melt flow and method for the preparation thereof|
|EP0699714A2||14 Ago 1995||6 Mar 1996||General Electric Company||Compositions of poly(phenylene ether) and polyester resins|
|EP2145919A1||25 Ene 2007||20 Ene 2010||General Electric Company||Molding compositions containing polycarbonate and modified polybutylene terephthalate(PBT) random copolymers derived from polyethylene terephthalate (PET)|
|EP2169007A1||27 Abr 2009||31 Mar 2010||Sabic Innovative Plastics IP B.V.||Method for preparing a poly(arylene ether) composition with improved melt flow|
|WO2006127245A2||8 May 2006||30 Nov 2006||General Electric Company||Low gloss thermoplastic composition|
|WO2009009731A2||11 Jul 2008||15 Ene 2009||Sabic Innovative Plastics Ip B.V.||Thermoplastic poly(arylene ether)/polyester blends and articles thereof|
|WO2011077297A1||29 Nov 2010||30 Jun 2011||Sabic Innovative Plastics Ip B.V.||Methods for the preparation of a poly(arylene ether) polysiloxane multiblock copolymer|
|WO2013027167A2||20 Ago 2012||28 Feb 2013||Sabic Innovative Plastics Ip B.V.||A molded article having enhanced aesthetic effect and method and system for making the molded article|
|Clasificación de EE.UU.||524/539, 525/444, 260/DIG.24|
|Clasificación internacional||C08L67/00, C08G63/52, C08G63/199, C08G63/20, C08G63/18, C08G63/00|
|Clasificación cooperativa||Y10S260/24, C08G63/18, C08G63/52, C08L67/00, C08G63/20|
|Clasificación europea||C08L67/00, C08G63/20, C08G63/18, C08G63/52|